The method of obtaining the ball of the catalyst in the cracking of crude oil

 

The method of obtaining the ball of the catalyst in the cracking of crude oil, comprising a mixture of aqueous solutions of aluminum sulfate, sodium silicate and suspensions of zeolite NaY with the module of 4.5 to 9.5 in the mixer with the formation of the aluminosilicate zeolite-containing Hydrosol, which then coagulates in the hydrogel pellet form in a layer of mineral oil; syneresis in a sodium sulphate solution; activating solution of nitrate or ammonium sulphate, activated with a solution of nitrate of rare earth elements; washing, drying and calcination in a stream of air-steam mixture. When this catalyst is formed in mineral oil with a density of 900-910 kg/m3and a viscosity of 25-50 mm2/s at 50°C with a shift in a big way maximum distribution of the granules of the catalyst in size after washing before drying pre are steamed with live steam, and calcining are within 68-75 h in steam-air mixture with the water vapor content of 18 to 30 volume%. Obtain a catalyst of high catalytic activity, low shrinkage, low cracking, and improved economic performance. 1 C.p. f-crystals, 3 tab., 2 Il.

The invention relates to the refining, in particular to an str is in the catalyst (U.S. Pat. U.S. No. 3312615, CL 208-120, 1967) containing crystalline aluminosilicate (zeolite Y), silicate matrix and inert fillers, in which the zeolite in sodium and rare earth cation forms in an amount of from 1 to 7 wt.% injected into the amorphous aluminosilicate matrix in the molding process of the balls in the oil column. The obtained hydrogel beads is subjected to activation by a mixture of solutions of ammonium sulfate and chlorides of rare earth elements, salts were washed off, dried in a steam drying apparatus at a temperature of 120-150°C for 3 hours, then treated with 100% steam at a temperature of 649°C for 30 h under a pressure of 1.2 MPa. The disadvantages of this method when using zeolite in the sodium cation form of low bulk density and strength of the catalyst.

A method of obtaining CSK (and.with. The USSR №389829, MKI 01 J 29/08, 1973) for the conversion of hydrocarbons by the introduction of a 15 wt.% zeolite NaY in 85% alumagrips in the process of forming the column with mineral oil. The composition alumagrips 93% SiOcand 7% Al2About3. Koagulirovannogo zeolite-containing hydrogel after incubation in a solution of sodium sulfate (syneresis) is treated with a solution of a basic salt of aluminum sulfate with XLE which are activated with a solution of a mixture of nitrates of rare-earth elements concentration of 1.0-1.2 g/l in terms of REE oxides. Then the beads are washed with steam condensate at a temperature of 50-52°C, dried at a temperature of 140-170°C and calcined at a temperature of 750°C for 12 hours in a current of steam-air mixture. The content of water vapor in a mixture of 40-45% by volume. The disadvantages of this method include the lack of durability of the catalyst and significant losses in the production process.

Closest to the technical essence and the achieved effect to the proposed technical solution is the way to obtain platinum source aluminosilicate zeolite catalyst (U.S. Pat. Of the Russian Federation No. 2167908, MKI With 10 G 11/05, 01 J 29/12, 2001), consisting of 5-20 wt.% zeolite NaY with the module (molar ratio of silica/ alumina), equal to 4.5 to 9.5 and 80-95% of the aluminosilicate framework. The catalyst according to the method of preparing a mixture of aqueous solutions of aluminum sulfate acidified with sulfuric acid (alumina content of 15-25 kg/m3; the content of sulfuric acid 50-80 kg/m3), sodium silicate (liquid glass) concentration of NaOH 1.4 to 1.8 kg-EQ/m3and water suspensions of zeolite NaY, containing 30-110 kg/m3zeolite, with the formation of a Hydrosol, which then coagulates at 5-20°C and pH 7.5-8.5 in the hydrogel pellet form in a layer of mineral oil. The dal is within 12-36 hours and an aqueous solution of a mixture of nitrates of rare-earth elements concentrations of 1-5 kg/m3(calculated as oxides REE) within 24-36 h, or their mixture, washed with condensate water containing iron cations from 0.01 to 0.5 kg/m3magnesium 0,001-0,5 kg/m3(calculated as metal oxides) at 35-60°C for 8-24 h, dried at 110-190°C and calcined at 650-750°C for 12-24 h in a current of steam-air mixture with the water vapor content of 40% by volume. To reduce the allocation of carbon monoxide (11) with gases oxidative regeneration of the catalyst is injected platinum by adding hexachloroplatinic acid, H2tl6in a solution of aluminum sulfate in the amount is 0.0002-0.04 kg/m3(calculated as platinum) or in the number 0,0006-0,085 kg/m3(calculated as platinum) in aqueous suspension of zeolite. The disadvantages of this method are low bulk density, low strength, and significant losses in the form of an improper fraction small balls. This fraction is quickly taken out of the reactor cracking and irretrievably lost. This leads to a significant consumption of catalyst for additional load (1.9 to 2.5 kg/ton of processed raw materials and more). In addition, significant cracking of the pellets trademarks of catalyst in the process of operation (more than 75% of the total wear of the balls).

The objective of the proposed order is ionic composition and, as a consequence, the reduction of entrainment of the catalyst during operation, reducing cracking (marriage drying) in the production process, shrinkage and cracking during operation, as well as increased activity and selectivity of the catalyst.

The problem is solved in that in the method of obtaining the ball of the catalyst in the cracking of crude oil, comprising a mixture of aqueous solutions of aluminum sulfate, sodium silicate and suspensions of zeolite NaY with the module of 4.5 to 9.5, with the formation of the aluminosilicate zeolite-containing Hydrosol, which then coagulates in the hydrogel pellet form in a layer of mineral oil, syneresis in a sodium sulphate solution, the activation of an aqueous solution of nitrate or ammonium sulfate, activation aqueous solution of nitrates of rare-earth elements or their mixture; washing, drying and calcination in a stream of steam-air mixture, the catalyst is formed with a shift of the maximum of the distribution of granules toward larger sizes by increasing the flow of the mixture for forming the column, filled with mineral oil with density 900-910 kg/m3and a viscosity of 25-50 mm2/s at 50°C; after washing the salts granules previously are steamed live steam with a temperature of 120-220°C for 0.5 to 1.0 hours, and partovy the catalyst contains 7-10 wt.% zeolite has a composition, wt.%:

Aluminum oxide 8-10

The oxides of rare earth elements 0,5-3,0

The iron oxide of 0.01-0.4

The sodium oxide 0,01-0,5

Silica Rest

The larger size of the formed hydrogel granules compared with the comparison sample ceteris paribus leads to a significant increase in marriage when drying. In accordance with this invention to reduce spoilage during the drying of wet beads of catalyst after activation and flushing steam condensate is put on the tape of the drying unit and immediately treated with live steam. Sharp steam increases the temperature in the zone of steaming 10-15Compared to the device without the introduction of steaming. The catalyst calcined at prokalochnoj apparatus in the current steam-air mixture with water vapor content 18-30% by volume at a temperature of 650-750With over 68-75 hours.

The proposed solution is illustrated by examples that make up the essence of the proposed method of manufacture of the ball cracking catalyst, but is not limited to them.

Example 1. Obtaining catalyst according to the present method in terms of industrial production.

1.1 Preparation of an aqueous suspension of zeolite NaY. Water dispersion of the zeolite suspension process for dispersing device to obtain the content of particles less than 8 mm not less than 95 wt.%; less than 4 μm is not less than 85 wt.%. The solid content in the suspension of zeolite 30-150 kg/m3.

1.2 Preparation of working solutions.

a) a Solution of sodium silicate (liquid glass). Prepare sodium silicate concentration of NaOH of 1.6-1.8 kg-EQ/m3and silicate modulus equal to 2.85-3,10, by dissolving silicate blocks in technical water under pressure, followed by filtration and dilution with water.

b) a Solution of aluminum sulphate. A solution prepared by dissolving aluminum hydroxide in sulphuric acid. The concentration of working solution on alumina 15-25 kg/m3the content of free sulfuric acid 50-80 kg/m3.

C) a Solution of a mixture of nitrates of rare-earth elements is prepared with a concentration of 0.2-3.0 kg/m3the REE oxides.

g) a Solution of ammonium sulfate is prepared by concentration of 5-20 kg/m3by dissolving the solid salt in water followed by filtration.

1.3. Forming catalyst.

A solution of sodium silicate (liquid glass) (first thread), aqueous suspension of zeolite (WCC) (second thread) and acidified with a solution of aluminum sulfate (third thread) separately cooled in heat exchangers to a temperature of 5-15And mixed in a three-flow smesitel to form in the oil column.

The molding conditions:

The oil forming the turbine:

The density of the oil 0.900 for 0,910 kg/m3

The kinematic viscosity at 50°C, mm2/with 25-50

Oil temperature when formed,°C 20-22

The temperature of the sodium silicate solution,°C 4-6

The temperature of the acidic solution of aluminum sulfate,°C 6-8

The temperature of the WCC,°C 4-6

Temperature Zola after mixing 5-15

the pH of the mixture prior to gelation 7,5-8,5

The temperature of the molding oil,°C 20-22

Control of the dimensions of the hydrogel beads in the forming process: when sizing beads on a sieve with the hole diameter of 12 mm is not more than 15-18%, and on a sieve with the hole diameter of 6 mm is not more than 3-5%. Particles are wrong (disc-shaped or lenticular) form no.

1.4. Thermochemical activation.

These granules are transported in the tank for conducting thermochemical activation (hereinafter - VAT) transport stream of water containing the sodium sulfate concentration of 30-50 kg/m3and stand there for 6-24 hours. Next Chan is connected to the first activation of ammonium sulfate solution the last in a chain of 5 tanks so that the subsequent input VAT connected to the output of the previous one. To input the first Chan serves sulfate solution is the atur 35-60°C. After the first activation (20 h) switch the tank at the second activation.

The second activation is carried out with a solution of a mixture of nitrates REE concentrations of 1-5 kg/m3within 8-16 hours in a chain of 3 tanks.

The solution flow rate of 1.1-1.3 m3/m3in the hour. The content of the cerium oxide used in the solution is not more than 2.5 wt.% the amount of oxides of rare-earth elements; the content of ammonium nitrate is not more than 20 wt.%. After the second activation connect the tub to wash out salts.

Leaching is carried out in a chain of 3 tanks within 8-24 hours steam condensate. The flow of wash water to 1.1-1.3 m3/m3per hour at a temperature of 35 to 60°C.

At the end of the washing added to the wash water solution of hexachloroplatinic acid based 2-5 ppm of metallic platinum on the dry catalyst in two stages.

1.5. Steaming wet granules.

The washed pellets of catalyst fed to the tape industrial devotional drying apparatus and are steamed in the first zone with live steam with a temperature of 120-220°C within 0.3 h Pairs served down at the wet layer of balls through the distribution manifold valve, located at a distance of 0.5 m from the surface layer of balls and creating uniform airflow layer. The scheme of the comb shown in Fig. 1. The steam consumption of Alas in this area without the introduction of steaming, but without the “bloat” layer wet balls excess steam flow.

1.5. Drying and calcination of the catalyst.

The catalyst was dried for 3-5 hours while gradually raising the temperature zones of the drying unit from 82-85 to 160-190°C and rigidly normalized moisture content of the coolant in each of the zones. The residual moisture content in the dry granules of the catalyst of 9.2-9.6 wt.%, considering IFR at 800°C.

The catalyst is calcined at a temperature of 680-720°C in a steam-air mixture with the water vapor content of 18% by volume within 68-75 PM

Example 2. The catalyst was prepared analogously to example 1. After washing the pellets are steamed live steam within 0,8 including Residual moisture content in the catalyst after drying of 10.3 wt.%. The catalyst calcined 68-75 h in a current of steam-air mixture with the water vapor content of 18% vol.

Example 3. The catalyst was prepared analogously to example 1. After washing the pellets are steamed 0.5 hours the Residual moisture content in the catalyst after drying at 9.0 wt.%. The catalyst calcined 68-75 h in a current of steam-air mixture with the water vapor content of 30 vol.%

Example 4. The catalyst was prepared analogously to example 1. After washing the pellets are steamed during 0,8 including Residual moisture content in kataliza 30 vol.%

Example 5 (prototype). Granules formed into a column filled with turbine oil with a density 891 kg/m3, viscosity at 50°C 22 mm2/S. the Distribution of wet balls when formed: on a sieve with the hole diameter of 10 mm is delayed no more than 15% of the mass of balls; on the sieve with a diameter of holes 5 mm - no more than 3%. The second activation is carried out with a solution of a mixture of nitrates of rare-earth elements and ammonium nitrate concentration of the REE oxides of 1.1-2.5 kg/m3with the content of cerium oxide 55-60% to the sum of the REE oxides and washed beads steam condensate at a temperature of 35-60°C. After washing the condensate pellets are steamed. The catalyst is dried at a temperature of 72-170°C until the moisture content IFR at 800°C of 6.5-7.5 wt.% and calcined at a temperature of 680-720°C for 12 h in a current of steam-air mixture with the water vapor content of 40 vol.%

Example 6. Forming and distribution of wet balls the size is similar to example 1. After washing the pellets are steamed. The residual moisture content in the catalyst after drying 8.0 wt.%. The catalyst was calcined for 12 h in a current of steam-air mixture with the water vapor content of 40 vol.%

Example 7. Granules formed into a column filled with turbine oil density 891 kg/m3, viscosity at 50°C 22 mm2/s Repreany composition is increased due to the inclusion of larger particles without displacement of the maximum of the distribution). In the molded mass of large granules observed many particles incorrect (lenticular) form. After washing the salts balls are steamed not. The residual moisture content in the catalyst after drying of 7.2 to 8.0 wt.%. The catalyst was calcined for 12 h in a current of steam-air mixture with the water vapor content of 40 vol.%

Example 8. Ball catalysts obtained in examples 1-7, experience according OST 38.01176-79. Before laboratory tests on catalytic activity and selectivity of the catalysts treated with 100% steam at 750°C for 6 h Catalytic activity determined at a temperature of 460°C and space velocity of the feedstock 1.5 h-1. As raw materials use standard raw material: careinogenesis fraction of Krasnodar oil (density at 20°C 862 kg/m3; initial boiling point of 203°C; 10% To 238°C; 50% - 275°C; 90% To 323°C; 96% - 336°C).

The catalysts obtained in examples 1, 5, used in the process of cracking of vacuum gasoil Permian oil (density 889 kg/m3; initial boiling point 254°C; the temperature of the end of the boil 447°C; sulphur content 1.31 wt.%). The process carried out in laboratory scale fixed bed of catalyst at a temperature of 460°C and volume RMSE is abilitati change amount of the catalyst before and after treatment, % vol. Determine the value of marriage when dried, wt.%, by selecting and weighing the chips formed during the drying process.

Determine the safety of pellets calcined catalyst to cracking during operation by boiling in water, %, as a proportion of whole pellets remaining after boiling in water for 10 minutes This value corresponds to the production data intact granules to cracking in the condition of catalytic cracking of heavy vacuum gas oil industrial plant type 43-102 (100% preservation of the catalyst during operation correspond to at least 60% of the security model method. Abrasion loss in the operation of the catalyst is not more than 25% of total losses).

The test results of the obtained catalysts are shown in Fig.2 and in tables 1-3.

From table 1 and Fig. 2 shows that the maximum distribution of the catalyst particles by the present method, in contrast to the prototype does not move in the direction of fines.

From examples 1-7 and tables 1-3 shows that the formation of granules in the column with mineral oil density 900-910 kg/m3and elm is the second of 12 mm is not more than 15%, and on a sieve with the hole diameter 6 mm, not more than 3% of all particles, the maximum of the distribution of particle sizes is shifted by 10-20% higher compared to the prototype; activation of ammonium sulfate solution; activating solution mixture of nitrates REE, rinsing, steaming washed granules passing a stream of steam, drying and calcination of the catalyst during 68-75 h - steam-air mixture with water vapor content 18-30% volume - allows you to get the ball catalyst for the cracking of crude oil, which has low shrinkage and cracking during operation, high activity and selectivity, as well as the improved efficiency of production by reducing the amount of waste.

From examples 1, 4 and 7 shows that the shift of the maximum of the size distribution during forming hydrogel granules instead of simply increasing the share of large granules in the mixture significantly improves the output quality of the catalyst.

Example 1-7 shows that steaming wet balls in the first zone of the drying apparatus with live steam with a temperature of 170-220°C for 0.5 to 1.0 h and calcination of the catalyst at a temperature of 680-720°C in a steam-air mixture with water vapor content 18-3 is.

Claims

1. The method of obtaining the ball of the catalyst in the cracking of crude oil, comprising a mixture of aqueous solutions of aluminum sulfate, sodium silicate and suspensions of zeolite NaY with the module of 4.5 to 9.5 in the mixer with the formation of the aluminosilicate zeolite-containing Hydrosol, which then coagulates in the hydrogel pellet form in a layer of mineral oil, syneresis in a sodium sulphate solution, the activation solution of nitrate or ammonium sulphate, activated with a solution of nitrate of rare earth elements, washing, drying and calcination in a stream of steam-air mixture, wherein the catalyst is formed in mineral oil with a density of 900-910 kg/m3and a viscosity of 25-50 mm2/s at 50°C with a shift in a big way maximum distribution of the granules of the catalyst in size after washing before drying pre are steamed with live steam, and calcining are within 68-75 h in air-steam mixture with water vapor content 18-30% vol.

2. The method according to p. 1, characterized in that, before drying the pre-steaming uniform flow of steam passing through the layer of wet pellets, it is preferable to increase the temperature of the catalyst layer at 10-15°C, in accordance with the

 

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